KR20170015975A - Siloxane composition and method for producing same - Google Patents

Abstract

There is provided a siloxane composition exhibiting a physical property intermediate between a dimethylpolysiloxane oil and a gel-like siloxane cross-link, having fluidity or being dissolved in a solvent to exhibit fluidity, and a process for producing the same. An organopolysiloxane having a weight average molecular weight of 5,000 to 300,000,000 and containing 0.1 to 50 mol of a silane coupling agent per 1,000 mol of siloxane units, obtained by subjecting a specific organopolysiloxane raw material to an addition reaction in a large excess solvent of 8 times or more the mass of the raw material Wherein the crosslinked product is dissolved in a solvent.

Description

[0001] SILOXANE COMPOSITION AND METHOD FOR PRODUCING SAME [0002]

The present invention relates to a siloxane composition having fluidity indicating the physical properties intermediate between a dimethylpolysiloxane oil and a gel-like siloxane cross-link, and a process for preparing the same.

The gelated organopolysiloxane bridges are used for cosmetics, coating of connection parts of electric wiring, etc., but all are solid materials having no fluidity. Therefore, it does not dissolve in a solvent, and a long-time grinding step is required in order to blend it into a cosmetic or a resin.

Silicone oil dispersions of silicone gel are used for cosmetics. This product is once made by addition reaction of solid state silicone gel, and is dispersed in silicone oil while pulverizing. This manufacturing method requires a lot of hands. In the case of a solid-phase silicone gel, even if unreacted functional groups are present in the vicinity of a solid portion due to the reaction, the adverse reaction does not proceed. The crosslinking density changed, and the control of the physical properties was difficult.

In the case of plastic, a silicone oil or silicone gum having a high degree of polymerization is dispersed in a resin for the purpose of improving fluidity at the time of molding, preventing contamination, and imparting sliding properties. Silicone oil having a low degree of polymerization has excellent fluidity and sliding properties, but silicone oil bleeds out to the surface, resulting in smoothness on the surface. For this reason, a silicon having a high degree of polymerization is used, but in order to uniformly disperse the silicon, it is necessary to make masterbatches in advance. In addition, since most of the added silicon is buried in the resin, only a part of the surface is involved in the action, and the efficiency is poor. On the other hand, when a solid-state silicone gel or resin is used, many components remain in the resin and compatibility with the resin is poor, resulting in poor dispersion and mechanical strength in many cases. Also, the surface modification effect is insufficient.

On the other hand, no method for synthesizing a compound exhibiting physical properties intermediate between silicone gel and silicone oil has been reported.

Further, as the prior art related to the present invention, the following documents can be cited.

Japanese Patent Application Laid-Open No. 05-140320

Disclosure of the Invention The present invention has been made in view of the above circumstances and provides a siloxane composition showing fluidity between a dimethylpolysiloxane oil and a gel-like siloxane crosslinked material and having fluidity or being dissolved in a solvent, .

As a result of intensive studies on organopolysiloxane crosslinked materials, the present inventors have found that by carrying out addition reaction of a specific raw material in a large amount of solvent of 8 times or more the mass of the raw material, Siloxane compositions can be synthesized, and the present invention has been accomplished.

Accordingly, the present invention provides the following siloxane compositions and methods for their preparation.

[One]

An organopolysiloxane having a structure represented by the following formula (1) and an organohydrogenpolysiloxane having a structure represented by the following formula (2) are mixed with the total of the polysiloxanes represented by the formulas (1) and (2) An organopolysiloxane crosslinked product obtained by a hydrosilylation reaction using a platinum group metal compound in a solvent of 8 times or more the mass of the polymer and having a weight average molecular weight of 5,000 to 300,000,000 and containing 0.1 to 50 mol of a silane coupling agent per 1,000 mol of siloxane unit Wherein the siloxane composition is dissolved in the solvent.

M _α M ^Vi _β D _γ D ^Vi _δ T _ε T ^Vi _ζ Q _η (1)

M _θ M ^H _ι D _κ D ^H _λ T _μ T ^H _ν (2)

(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is PSiO _3/2, M ^H is _{R 2 HSiO 1/2, D} H is RHSiO _2/2, T ^H is HSiO _3/2, Q is SiO _4/2, R is not having an aliphatic unsaturated bond, each independently An unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms, and P is an alkenyl group represented by - (CH ₂ ) _a -CH═CH ₂ (a is 0 or an integer of 1 to 6) δ, ζ, η, θ, ι, κ, λ, μ and ν are independently 0 or positive numbers and β, δ and ζ do not become 0 at the same time, β + δ + ζ≥2, and ι, λ and ν are not 0 at the same time, and ι + λ + ν≥2.

[2]

The siloxane composition according to [1], wherein 1? +? +? +?? 1,000 in the formula (1), and 1?? +? + Mu? 200 in the formula (2)

[3]

The siloxane composition according to [2], wherein in the formula (1), 1??? 1.000, and in the formula (2), 1?

[4]

The siloxane composition according to any one of [1] to [3], wherein the solvent contains an organic solvent selected from toluene, hexane, xylene and methyl ethyl ketone.

[5]

Solvent octamethyl tetra siloxane, deca-methylpentanoyl siloxane, formula M ₂ D _n (M is R ₃ SiO _1/2 denotes a unit, D is R ₂ SiO _2/2 denotes a unit, R is an aliphatic, each independently An unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms which does not have an unsaturated bond and n is an integer of 0 to 200) and a linear siloxane represented by the formula M _{2 + m} D _n T _m is selected from the branched siloxane represented by (m, D, n is such, T is RSiO _3/2 denotes a unit, R is as defined above. m is an integer a. 1 to 10 described above) Ogaki The siloxane composition according to any one of [1] to [3], wherein the siloxane is a non-siloxane.

[6]

The organopolysiloxane crosslinked product according to any one of [1] to [3]

M _{? '} M ^Vi _?' D _{? '} D ^Vi _?' T _{? '} T ^Vi _?' (3)

(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is ₃ PSiO _{/ 2} and, R are each independently an aliphatic unsaturated bond that the carbon atom number of 1 to 12 or an unsubstituted monovalent hydrocarbon group having no substitutions, and P is _{- (CH 2) a -CH =} CH 2 (a is 0 or an integer of 1 to 6), and each of α ', β', γ ', δ', ε 'and ζ' is independently 0 or a positive number, and α '+ β' +? '+?' +? '+?'? 200).

Wherein the content of the organopolysiloxane is 0.1 to 40 times the mass of the organopolysiloxane crosslinked product.

[7]

The organopolysiloxane crosslinked with a kinematic viscosity 20mm ² / s [1] ~ a viscosity at 25 ℃ in the case where 30% by weight dissolved in a dimethyl polysiloxane of (25 ℃), characterized in that 100~2,000,000mPa · s [6] The siloxane composition according to any one of [1] to [6].

[8]

The siloxane composition according to any one of [1] to [7], which has a viscosity at 25 ° C of 50 to 1,000,000 mPa · s when 30% by mass of an organopolysiloxane crosslinked product is dissolved in toluene.

[9]

1], wherein the weight average molecular weight of the organopolysiloxane represented by the formula (1) is from 260 to 74,874 and the weight average molecular weight of the organohydrogenpolysiloxane represented by the formula (2) is from 208 to 15,414. To (8) above.

[10]

The siloxane composition according to any one of [1] to [9], wherein the residual SiH group content calculated from the amount of hydrogen gas generated by the addition of alkali is 0.001 mol / 100 g or less.

[11]

An organopolysiloxane having a structure represented by the following formula (1) and an organohydrogenpolysiloxane having a structure represented by the following formula (2) are mixed with the total of the polysiloxanes represented by the formulas (1) and (2) An organopolysiloxane crosslinked product having a weight average molecular weight of 5,000 to 300,000,000 and containing 0.1 to 50 mol of a silane coupling agent per 1,000 mol of the siloxane unit by a hydrosilylation reaction using a platinum group metal compound in a solvent of 8 times or more the mass To obtain a siloxane composition.

M _α M ^Vi _β D _γ D ^Vi _δ T _ε T ^Vi _ζ Q _η (1)

M _θ M ^H _ι D _κ D ^H _λ T _μ T ^H _ν (2)

(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is PSiO _3/2, M ^H is _{R 2 HSiO 1/2, D} H is RHSiO _2/2, T ^H is HSiO _3/2, Q is SiO _4/2, R is not having an aliphatic unsaturated bond, each independently An unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms, and P is an alkenyl group represented by - (CH ₂ ) _a -CH═CH ₂ (a is 0 or an integer of 1 to 6) δ, ζ, η, θ, ι, κ, λ, μ and ν are independently 0 or positive numbers and β, δ and ζ do not become 0 at the same time, β + δ + ζ≥2, and ι, λ and ν are not 0 at the same time, and ι + λ + ν≥2.

[12]

An organic solvent selected from toluene, hexane, xylene and methyl ethyl ketone as a solvent is used to obtain an organopolysiloxane crosslinked product, and then an organopolysiloxane having a low viscosity is added as a solvent. And removing the solvent by heating to remove the organic solvent. [11] The method for producing a siloxane composition according to [11].

[13]

(3), wherein the organopolysiloxane having a low viscosity is represented by the following formula

M _{? '} M ^Vi _?' D _{? '} D ^Vi _?' T _{? '} T ^Vi _?' (3)

(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is ₃ PSiO _{/ 2} and, R are each independently an aliphatic unsaturated bond that the carbon atom number of 1 to 12 or an unsubstituted monovalent hydrocarbon group having no substitutions, and P is _{- (CH 2) a -CH =} CH 2 (a is 0 or an integer of 1 to 6), and each of α ', β', γ ', δ', ε 'and ζ' is independently 0 or a positive number, and α '+ β' +? '+?' +? '+?'? 200).

Wherein the organosiloxane is an organopolysiloxane represented by the following formula [12].

The siloxane compositions of the present invention can exhibit novel properties for various applications due to their unprecedented physical properties. Examples of usable applications include a silicone gel for cosmetics which can be easily and inexpensively synthesized with a soft touch, a silicone compounded plastic molding having no feeling of surface smear, an anti-mist agent produced at high speed coating of release silicone, And the like.

The siloxane composition of the present invention comprises an organopolysiloxane crosslinked product and a solvent, and the organopolysiloxane crosslinked product of the present invention is obtained by reacting an organopolysiloxane having a structure represented by the following formula (1) Of the total mass of the polysiloxane represented by the formula (1) and the polysiloxane represented by the formula (2) by a hydrosilylation reaction using a platinum catalyst in a solvent in which the organohydrogenpolysiloxane having a structure represented by the formula Average molecular weight of 5,000 to 300,000,000, and contains 0.1 to 50 mol of a silane coupling agent per 1000 mol of siloxane unit.

M _α M ^Vi _β D _γ D ^Vi _δ T _ε T ^Vi _ζ Q _η (1)

M _θ M ^H _ι D _κ D ^H _λ T _μ T ^H _ν (2)

(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is PSiO _3/2, M ^H is _{R 2 HSiO 1/2, D} H is RHSiO _2/2, T ^H is HSiO _3/2, Q is SiO _4/2, R is not having an aliphatic unsaturated bond, each independently An unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms, and P is an alkenyl group represented by - (CH ₂ ) _a -CH═CH ₂ (a is 0 or an integer of 1 to 6) δ, ζ, η, θ, ι, κ, λ, μ and ν are independently 0 or positive numbers and β, δ and ζ do not become 0 at the same time, β + δ + ζ≥2, and ι, λ and ν are not 0 at the same time, and ι + λ + ν≥2.

First, an organopolysiloxane having a structure represented by the following formula (1) and an organohydrogenpolysiloxane having a structure represented by the following formula (2) will be described.

M _α M ^Vi _β D _γ D ^Vi _δ T _ε T ^Vi _ζ Q _η (1)

M _θ M ^H _ι D _κ D ^H _λ T _μ T ^H _ν (2)

In the formulas (1) and (2), M, M ^Vi , D, D ^Vi , T, T ^Vi , M ^H , D ^H , T ^H and Q are each a unit shown below.

M: R ₃ SiO _1/2

^{_{M Vi: R 2 PSiO 1/}} 2

D: R ₂ SiO _2/2

D ^Vi: RPSiO _2/2

T: RSiO _3/2

T ^Vi: PSiO _3/2

^{_{M H: R 2 HSiO 1/}} 2

D ^H: RHSiO _2/2

T ^H: HSiO _3/2

Q: SiO _4/2

In the above formulas, each R independently represents an unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, having no aliphatic unsaturated bond. For example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group; Cycloalkyl groups such as cyclohexyl group; An aryl group such as a phenyl group, a naphthyl group, and a tolyl group; Or a part of hydrogen atoms bonded to the carbon atoms of these groups is substituted with a halogen atom, a cyano group, a hydroxyl group, or the like. It is preferable that at least 50 mol% of the total number of R is a methyl group in terms of lowering the peeling force.

And P is an alkenyl group represented by - (CH ₂ ) _a -CH = CH ₂ (a is 0 or an integer of 1 to 6).

?,?,?,?,?,?,?,? are independently 0 or a positive number. ? +? +? Is 2 or more, preferably 2 to 10, more preferably 2 to 5, and?,?, And? Are not 0 at the same time And ι + λ + ν is 2 or more, preferably 2 to 10, more preferably 2 to 5.

Further,?,?,? And? Are not 0 at the same time, and in particular, from the viewpoint of the content of the ethylenic bond,? +? +? +? Is preferably 1 to 1,000, more preferably 10 to 500, More preferably 50 to 400. In this case, in view of the content of the ethylenic bond,? Is preferably 1 to 1,000, more preferably 10 to 500, and still more preferably 50 to 400. Further,? Is preferably 0 to 20, more preferably 0 to 10, still more preferably 0 to 5. ? is preferably 0 to 50, particularly 0 to 10, and? is preferably 0 to 5, particularly 0 to 1.

On the other hand,?,?, And? Do not become 0 at the same time, and similarly, from the viewpoint of the content of the ethylenic bond,? +? +? Is preferably 1 to 200, more preferably 10 to 150, Lt; / RTI > In this case, κ is preferably 1 to 200, more preferably 10 to 150, and still more preferably 20 to 100. ? is preferably 0 to 20, more preferably 0 to 10, still more preferably 0 to 5. mu is preferably from 0 to 50, more preferably from 0 to 10.

The organopolysiloxane represented by the formula (1) is an organopolysiloxane having two or more, preferably 2 to 10, silicon atom-bonded alkenyl groups in one molecule.

The weight average molecular weight of the organopolysiloxane is preferably from 260 to 74,874, and more preferably from 408 to 7,586. If the weight average molecular weight is too large, the gel may become soft and tacky and may be difficult to handle. Therefore, the Q unit is preferably 1 or less, more preferably 0. In addition, the weight average molecular weight can be measured by weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) analysis (solvent: toluene) (the same applies hereinafter).

Specific examples of such organopolysiloxanes include a siloxane having a terminal alkenyl group, a siloxane having a side chain alkenyl group, a siloxane having a terminal end and a side chain alkenyl group, and a siloxane having a terminal alkenyl group having a terminal double end. ^{_{, M Vi 2 D γ, M}} 2 D γ D Vi δ, M Vi 3 D γ T 1, M Vi 4 D γ T 2, M Vi 2 D γ D Vi δ, M Vi 2 D γ Q 1, M α D _? D ^Vi _? T ^Vi _? Where? Is from 1 to 1,000, in particular from 10 to 500, in particular from 50 to 400,? Is from 2 to 20, in particular from 2 to 10, in particular from 2 to 5, 1 to 10, particularly 1 to 6). More specific structure examples of ^{_{M Vi 2 D 10, M Vi}} 2 D 100, M 2 D 27 D Vi 3, M 2 D 97 D Vi 3, M 2 D 26 D Vi 4, M 2 D 25 D Vi 5, M 2 D ₂₄ D ^Vi ₆ , M ₂ D ₉₆ D ^Vi ₄ , M ₂ D ₉₅ D ^Vi ₅ , M ^Vi ₃ D ₁₀₀ T ₁ , M ^Vi ₄ D ₁₀₀ T ₂ , M ^Vi ₂ D ₉₇ D ^Vi ₁ , M ^Vi ₂ D ₉₅ D ^Vi ₃ , and M ₃ D ₉₃ D ^Vi ₃ T ^Vi ₁ .

The vinyl group content is 0.001 to 1 mol / 100 g, more preferably 0.01 to 0.1 mol / 100 g.

The organohydrogenpolysiloxane represented by the formula (2) is an organohydrogenpolysiloxane having two or more, preferably 2 to 100, silicon atom-bonded hydrogen atoms (SiH groups) in one molecule. The SiH group of the organohydrogenpolysiloxane and the vinyl group of the organopolysiloxane represented by the formula (1) are subjected to an addition reaction to form an organopolysiloxane crosslinked product.

The weight average molecular weight of the organohydrogenpolysiloxane is preferably from 208 to 15,414, and more preferably from 282 to 7,534. If the weight average molecular weight is too small, the crosslinking density becomes high, which may cause gelation or solidification. When the weight average molecular weight is too large, the gel may become soft and tacky, making handling difficult.

Specific examples of the organohydrogenpolysiloxane include a siloxane having both terminal hydrogen groups, a siloxane having side chain hydrogen groups, a siloxane having both terminal and side chain hydrogen groups, a siloxane having both ends and side chain hydrogen groups, etc. M ^H ₂ D _κ , M ₂ D ^H _λ , M ₂ D _κ D ^H _λ , M ^H ₂ D _κ D ^H _λ , M ^H ₃ D _κ T ₁ , and M ^H ₄ D _κ T ₂ , M _θ D _κ D ^H _λ T ^H _ν (where κ is from 1 to 200, in particular from 10 to 150, in particular from 20 to 100, λ is from 1 to 20, in particular from 1 to 10, ,? is 3 to 22, in particular 3 to 12, in particular 3 to 7, v is 1 to 20, in particular 1 to 10, in particular 1 to 6). More specific examples thereof include M ^H ₂ D ₁₀ , M ^H ₂ D ₁₀₀ , M ₂ D ₂₇ D ^H ₃ , M ₂ D ₉₇ D ^H ₃ , M ₂ D ₂₆ D ^H ₄ , M ₂ D ₂₅ D ^H ₅ , M ₂ D ₂₄ D ^H ₆ , M ₂ D ₉₆ D ^H ₄ , M ₂ D ₉₅ D ^H ₅ , M ^H ₃ D ₁₀₀ T ₁ , M ^H ₄ D ₁₀₀ T ₂ , M ^H ₂ D ₉₇ D ^H ₁ , M ^H ₂ D ₉₅ D ^H ₃ , M ₃ D ₉₃ D ^H ₃ T ^H ₁ , and the like.

The SiH group content is preferably 0.01 to 10 mol / 100 g, and more preferably 0.01 to 1 mol / 100 g.

The amount of the organohydrogenpolysiloxane to be used is preferably such that the ratio (SiH group: alkenyl group) of the SiH group in the organohydrogenpolysiloxane to the alkenyl group in the organopolysiloxane represented by the formula (1) is 0.8: 1 To 1.8: 1, and more preferably 0.9: 1 to 1.6: 1.

The organopolysiloxane crosslinked product of the present invention is obtained by subjecting an organopolysiloxane having the structure represented by the formula (1) and an organohydrogenpolysiloxane having the structure represented by the formula (2) (Addition) reaction of a platinum group metal catalyst in a solvent in an amount of at least 8 times, preferably at least 10 times, more preferably at least 12 times the total mass of the organopolysiloxane represented by the formula Can be synthesized. This is a reaction added to the vinyl group in the organopolysiloxane having a structure represented by the formula (1) in the SiH group in the organohydrogenpolysiloxane represented by the formula (2) by the platinum group metal catalyst.

Here, as the platinum group metal catalyst, known catalysts used as an addition reaction catalyst may be used. Examples of the platinum group metal catalyst include platinum group, palladium, rhodium, and ruthenium catalysts, and among these, a platinum catalyst is preferably used. Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution or an aldehyde solution of chloroplatinic acid, and various olefin or vinyl siloxane complexes of chloroplatinic acid.

The amount of the platinum group metal catalyst to be added is a catalytic amount, but it is economical that the amount of the platinum group metal is in the range of 0.1 to 100 ppm based on the total amount of the organo polysiloxane having the alkenyl group and the organohydrogen polysiloxane And more preferably in the range of 0.5 to 5 ppm.

Examples of the solvent used in the synthesis of the organopolysiloxane crosslinked product in the present invention include organic solvents soluble in organopolysiloxanes such as toluene, hexane, xylene and methyl ethyl ketone (not containing a siloxane solvent) , octamethyl tetra siloxane, methyl deca low viscosity of the cyclic siloxane, such as penta siloxane, M ₂ D _n (M, D are as above. n is 0 to 200, preferably an integer of 1 to 50. ), such as a linear siloxane, ₂₊ m _m D _n T _m (m, D, T are as above. n is 0 to 200, preferably an integer of 1~50, m is 1 to 10, preferably (A siloxane solvent) such as a branched siloxane such as tetramethoxysilane, tetraethoxysilane, tetraethoxysilane, tetraethoxysilane, tetraethoxysilane or tetraethoxysilane.

The amount of the solvent used is 8 times or more, preferably 10 times or more and 50 times or less, and more preferably 12 times or more and 40 times or less the total mass of the organopolysiloxane represented by the above formulas (1) and (2). If the amount of the solvent to be used is too small, the molecular weight of the crosslinked organopolysiloxane increases excessively and gelation occurs. When the amount is too large, the molecular weight becomes excessively small, and there is no characteristic as a crosslinked product, resulting in characteristics close to oil.

Since the reaction by hydrosilylation proceeds at room temperature but is slow, the reaction temperature is preferably from 50 to 140 캜, particularly from 60 to 120 캜, and the reaction time is preferably from 1 to 8 hours, particularly from 2 to 5 hours.

The reaction can be confirmed by the amount of generated hydrogen gas, and is preferably 0.001 mol / 100 g or less, and more preferably 0.0001 mol / 100 g or less as the amount of residual SiH groups. The amount of hydrogen gas generation is determined by adding an aqueous alkali diluted with water to about 10 g of a sample and measuring the amount of hydrogen gas generated.

The organopolysiloxane crosslinked product obtained by the above reaction has a weight average molecular weight (Mn) of 5,000 to 300,000,000, preferably 5,000 to 12,000,000, and more preferably 7,000 to 500,000. This range is preferably 65 to 163,000, more preferably 90 to 6,760 in terms of average degree of polymerization. The weight average molecular weight can be determined as the weight average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis (solvent: toluene). When the weight average molecular weight is too large, the column for ultrahigh molecular weight TSKgel Super HM -H. ≪ / RTI > Further, the average degree of polymerization can be obtained from the obtained Si-NMR results (the same applies hereinafter).

The organopolysiloxane crosslinked product obtained by the above reaction has a content of the ethylenic bonds per 1,000 mol of the siloxane unit calculated from ¹ H-NMR of 0.1 to 50 mol, preferably 1 to 30 mol. If the content of the above-mentioned ethylenic bond is too small, the properties of the oil become close to that of the oil, and properties as a crosslinked product can not be obtained. If too much, the viscosity becomes excessively high and mixing may be difficult.

The viscosity of the organopolysiloxane crosslinked product obtained above at 25 캜 as measured using a B-type rotational viscometer is in the range of 100 to 2,000,000 mPas when 30% by mass is dissolved in dimethylpolysiloxane having a kinematic viscosity of 20 mm ² / s (25 캜) S, more preferably 300 to 160,000 mPa · s, still more preferably 500 to 100,000 mPa · s, particularly preferably 1,000 to 50,000 mPa · s, and further dissolving in toluene in an amount of 30% by mass , It is preferably 50 to 1,000,000 mPa · s, more preferably 100 to 130,000 mPa · s, still more preferably 300 to 50,000 mPa · s, and particularly preferably 500 to 10,000 mPa · s.

In the present invention, the organopolysiloxane crosslinked product can be used as a composition containing the solvent used in the above-mentioned reaction as it is, and the composition does not contain a solid and is a uniform oil phase.

Further, in the case of synthesis using an organic solvent such as toluene, it is possible to add a low viscosity organopolysiloxane as a solvent, and then distill off the organic solvent by heating under reduced pressure to obtain a composition containing no organic solvent have. This method is effective when an organopolysiloxane containing an alkenyl group is used as an organopolysiloxane having a low viscosity.

In this case, the pressure is preferably 0.01 to 50 mmHg, particularly 0.1 to 30 mmHg, and the heating conditions are preferably 30 to 5 hours at 50 to 150 占 폚, particularly 30 to 3 hours at 60 to 130 占 폚.

As the low viscosity organopolysiloxane, a compound having a structure represented by the following formula (3) is preferable.

M _{? '} M ^Vi _?' D _{? '} D ^Vi _?' T _{? '} T ^Vi _?' (3)

(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is . PSiO a _3/2, R is each independently an aliphatic unsaturated bond that the carbon number of the hydrocarbon which is unsubstituted or substituted 1 for 1 to 12 atoms having a hydrogen, there can be mentioned the same meanings as defined above in addition, P is - ( CH ₂ ) _a -CH = CH ₂ (a is 0 or an integer of 1 to 6), and each of α ', β', γ ', δ', ε 'and ζ' +? '+?' +? '? 200, preferably 10?? +?' +? '+?' +? '+?'?

Specific examples of such low-viscosity organopolysiloxanes include dimethylpolysiloxane having a viscosity of 1 to 1,000 mPa · s, dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of the molecular chain, methyl having a vinyl group at the side chain Dimethylpolysiloxane having a dimethylhydroxysilyl group at both ends thereof, phenylmethylpolysiloxane having a phenyl group at the side chain, and the like, preferably M ^Vi ₂ D ₁₀ , M ^Vi ₂ D ₁₀₀ , M _{^{2 D 27 D Vi 3, M}} 2 D 97 D Vi 3, M 2 D 26 D Vi 4, M 2 D 25 D Vi 5, M 2 D 24 D Vi 6, M 2 D 96 D Vi 4, M 2 D _{^{95 D Vi 5, M Vi 3}} D 100 T 1, M Vi 4 D 100 T 2, M Vi 2 D 97 D Vi 1, M Vi 2 D 95 D Vi 3, M 3 D 93 D Vi 3 T Vi 1 , etc. And a vinyl group-containing polysiloxane.

The amount of the low viscosity organopolysiloxane represented by the formula (3) is preferably 0.1 to 40 times, more preferably 0.1 to 20 times, and still more preferably 0.5 to 10 times the mass of the organopolysiloxane crosslinked product , Particularly preferably 0.5 to 5 times.

The use of the organopolysiloxane crosslinked product of the present invention is not limited to the use of a silicone gel for cosmetics which can be easily and inexpensively synthesized with a soft texture, a silicone compounded plastic molded article having no feeling of smoothness on the surface, An anti-mist agent, and a pressure-sensitive adhesive excellent in releasability.

Example

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, the following viscosities are all values measured at 25 DEG C using a B-type rotational viscometer.

In the following examples, the symbol representing the composition of the siloxane represents the following unit.

_{M: (CH 3) 3 SiO} 1/2

^{_{M H: (CH 3) 2}} HSiO 1/2

_{^{M Vi: (CH 2 = CH}} ) (CH 3) 2 SiO 1/2

_{D: (CH 3) 2 SiO} 2/2

_{^{D H: (CH 3) HSiO}} 2/2

_{^{D Vi: (CH 2 = CH}} ) (CH 3) SiO 2/2

_{T: (CH 3) SiO 3} /2

_{^{T Vi: (CH 2 = CH}} ) SiO 3/2

Q: SiO _4/2

[Example 1]

M ₂ D _{24 . 6} D side chain type methyl hydrogen polysiloxane represented by 10g ^H ₂ and M ^Vi _2. 48 g (SiH group: vinyl group = 1 mole: 1.083 mole) of a branched vinylmethylpolysiloxane represented by ₄ D _{147 .7} T _0.4 were mixed in 696 g of toluene (corresponding to 12 times the total mass of siloxane) A platinum catalyst for feeding polysiloxane was added in an amount of 2 ppm based on the total mass of the reaction system as platinum mass, and the temperature was raised. The reaction was carried out at a temperature of 80 캜 for 5 hours, and the amount of residual SiH groups converted from the amount of generated hydrogen gas (hereinafter the same) was 0 mol / 100 g.

The obtained product had a viscosity of 5.4 mPa · s and a weight average molecular weight of 52,000. The toluene was removed by distillation under reduced pressure, and the viscosity was 8,000 mPa · s. When the crosslinked product was dissolved in toluene in a concentration of 30% by mass, the viscosity was 110 mPa · s. The viscosity when the crosslinked product was dissolved in 30 mass% in the dimethylpolysiloxane of ² / s was 290 mPa 占 퐏. Also, the amount of the ethylenic bond per 1000 mol of the siloxane unit calculated from ¹ H-NMR was 11.1 mol.

696 g of a dimethylpolysiloxane having a vinyl group at both ends, represented by M ^Vi ₂ D _{66 .8,} was added to the reaction mixture, and the mixture was distilled under reduced pressure at 150 캜 for 3 hours under nitrogen bubbling under 10 mmHg to obtain a siloxane 100% composition.

[Example 2]

M ₂ D _{24 . 6} D side chain type methyl hydrogen polysiloxane represented by 10g ^H ₂ and M ^Vi _2. 48 g (SiH group: 1 mole: 1.083 mole) of a branched vinylmethylpolysiloxane represented by ₄ D _{147 .7} T _0.4 was added to 812 g of toluene (total mass of branched-chain methylhydrogenpolysiloxane and branched vinylmethylpolysiloxane , Platinum catalyst for feeding vinylmethylpolysiloxane was added in an amount of 2 ppm based on the total mass of the reaction system as platinum mass and the temperature was raised. The reaction was carried out at a temperature of 80 ° C for 5 hours, and the amount of residual SiH groups was 0.00004 mol / 100 g.

A viscosity of 4.0 mPa 占 퐏 was obtained and a weight average molecular weight of 43,000. The viscosity when toluene was removed by distillation under reduced pressure was 5,550 mPa 占 퐏; the viscosity when toluene was dissolved in 30 mass% of toluene was 80 mPa 占 퐏 , And the viscosity when the crosslinked product was dissolved in 30 mass% in dimethylpolysiloxane having a kinematic viscosity of 20 mm ² / s was 230 mPa · s. Also, the amount of the ethylenic bond per 1000 mol of the siloxane unit calculated from ¹ H-NMR was 11.1 mol.

696 g of dimethylpolysiloxane represented by M ₂ D ₂₇ was added to the reaction product, and the mixture was distilled under reduced pressure at 150 캜 for 3 hours under nitrogen bubbling under a pressure of 10 mmHg to obtain a 100% siloxane composition.

[Example 3]

M ₂ D _{24 . 6} D side chain type methyl hydrogen polysiloxane represented by 10g ^H ₂ and M ^Vi _2. 48 g (SiH group: vinyl group = 1 mole: 1.083 mole) of branched vinylmethylpolysiloxane represented by ₄ D _{147 .7} T _0.4 was added to 696 g of dimethylpolysiloxane represented by M ₂ D ₂₇ (side chain methylhydrogenpolysiloxane And 12 times the total mass of the branched vinylmethylpolysiloxane), a platinum catalyst for feeding vinylmethylpolysiloxane was added in an amount of 2 ppm based on the total mass of the reaction system as a platinum mass, and the temperature was raised. The reaction was carried out at a temperature of 80 ° C for 5 hours, and the amount of residual SiH groups was 0 mol / 100 g.

Obtained was an oil having a viscosity of 223 mPa 占 퐏, a weight average molecular weight of 150,000, a viscosity of 983,000 mPa 占 퐏 as a crosslinked product estimated by calculation from the product viscosity described above, and a viscosity when the crosslinked product was dissolved in 30 mass% The viscosity when the crosslinked product is dissolved in 30 mass% in dimethylpolysiloxane having a viscosity of 5,490 mPa, and a dynamic viscosity of 20 mm ² / s is 8,700 mPa.. Also, the amount of the ethylenic bond per 1000 mol of the siloxane unit calculated from ¹ H-NMR in the crosslinking component excluding M ₂ D ₂₇ was 11.2 mol.

[Example 4]

M ₂ D _{24 . 6} D ^H ₂ side chain type methyl hydrogen polysiloxane 10g and M ^Vi ₂ socks Monotype methyl vinyl polysiloxane represented by D ₁₅₀ represented by 58.9g of (SiH group: vinyl group = 1 mol 1.097 mol) M ₂ D ₂₇ (Corresponding to 12 times the total mass of the side-chain type methylhydrogenpolysiloxane and the vinyl-methylpolysiloxane of the horseshoe type), and then platinum catalyst for replicating the vinylmethylpolysiloxane was added as a platinum mass to the reaction system 2 ppm was added to the total mass, and the temperature was raised. The reaction was carried out at a temperature of 80 캜 for 5 hours, and the amount of residual SiH groups was 0 mol / 100 g.

The obtained product was an oil having a viscosity of 240 mPa · s and a weight average molecular weight of 130,000. The viscosity as a crosslinked product estimated by calculation from the above product viscosity was 590,000 mPa · s. The viscosity when the crosslinked product was dissolved in toluene in an amount of 30% The viscosity when the crosslinked product is dissolved in 30 mass% in the dimethylpolysiloxane having a kinematic viscosity of 20 mm ² / s at 3,500 mPa · s is 5,800 mPa · s. Further, the amount of the ethylenic bond per 1000 mol of the siloxane unit calculated from ¹ H-NMR in the crosslinking component excluding M ₂ D ₂₇ was 10.8 mol.

[Example 5]

10 g of a side chain type methylhydrogenpolysiloxane represented by M ₂ D ₂₇ D ^H ₃ and 76.2 g (SiH group: 1 mol: 1.069 mol) of a vinyl-terminated vinyl methyl polysiloxane represented by M ^Vi ₂ D ₁₄₄ were dissolved in M (Corresponding to 12 times the total mass of the side-chain methylhydrogenpolysiloxane and the side-chain methylhydrogenpolysiloxane) represented by the formula ₂ D ₂₇ , and thereafter the platinum catalyst for the vinylmethylpolysiloxane 2 ppm of platinum mass was added to the total mass of the reaction system, and the temperature was raised. The reaction was carried out at a temperature of 80 캜 for 5 hours, and the amount of residual SiH groups was 0 mol / 100 g.

The obtained product was an oil having a viscosity of 970 mPa · s and had a weight average molecular weight of 300,000. The viscosity as a crosslinked product estimated by calculation from the above product viscosity was 17,000,000 mPa · s. The viscosity when the crosslinked product was dissolved in 30% The viscosity when the crosslinked product is dissolved in 30 mass% in dimethylpolysiloxane having a viscosity of 73,400 mPa · s and a kinematic viscosity of 20 mm ² / s is 96,600 mPa · s. Further, the amount of the ethylenic bond per 1000 mol of the siloxane unit calculated from ¹ H-NMR in the crosslinking component excluding M ₂ D ₂₇ was 6.3 mol.

[Example 6]

10 g of the side chain type methylhydrogenpolysiloxane represented by M ₂ D ₂₄ D ^H ₄ and 109.3 g (SiH group: 1 mol: 1.069 mole) of both ends vinylmethylpolysiloxane represented by M ^Vi ₂ D ₁₄₄ were dissolved in M (Corresponding to 14 times the total mass of the side chain type methylhydrogenpolysiloxane and the horseshoe-shaped vinylmethylpolysiloxane) of dimethylpolysiloxane represented by ₂ D ₂₇ , and then a platinum catalyst for feeding vinylmethylpolysiloxane 2 ppm of platinum mass was added to the total mass of the reaction system, and the temperature was raised. The reaction was carried out at a temperature of 80 캜 for 5 hours, and the amount of SiH groups remaining was 0.00005 mol / 100 g.

The obtained product was an oil having a viscosity of 3,060 mPa · s and a weight average molecular weight of 400,000. The viscosity as a crosslinked product estimated by calculation from the above product viscosity was 202,400,000 mPa · s. The viscosity when the crosslinked product was dissolved in 30% by mass in toluene Of 765,000 mPa · s and a kinematic viscosity of 20 mm ² / s in a dimethylpolysiloxane having a viscosity of 907,000 mPa · s. Further, the amount of the ethylenic bond per 1,000 mol of the siloxane unit calculated from ¹ H-NMR in the crosslinking component excluding M ₂ D ₂₇ was 6.5 mol.

[Example 7]

M ^H ₂ D ₄₀ socks Monotype methylhydrogen polysiloxane 10g and M ₂ D ₂₇ D ^Vi ₃ branched vinyl methyl polysiloxane 20g represented by the represented by the (SiH group: vinyl group = 1 mol 1.083 mol) M ₂ (Corresponding to 16 times the total mass of the side-chain type methylhydrogenpolysiloxane and the vinyl-methylpolysiloxane in the hermetic form) of dimethylpolysiloxane represented by D ₂₇ , and then platinum catalyst for pumping vinylmethylpolysiloxane was mixed with platinum 2 ppm based on the total mass of the reaction system was added, and the temperature was raised. The reaction was carried out at a temperature of 80 캜 for 5 hours, and the amount of residual SiH groups was 0 mol / 100 g.

The obtained product was an oil having a viscosity of 2,320 mPa · s and a weight average molecular weight of 440,000. The viscosity as a crosslinked product estimated by calculation from the above product viscosity was 238,000,000 mPa · s. The viscosity when the crosslinked product was dissolved in 30% by mass in toluene And a viscosity of 903,600 mPa · s when 30 mass% of the crosslinked product is dissolved in a dimethylpolysiloxane having a kinematic viscosity of 20 mm ² / s is 1,053,000 mPa · s. Further, 21 mol of the silane coupling agent per 1000 mol of the siloxane unit calculated from ¹ H-NMR in the crosslinking component excluding M ₂ D ₂₇ was obtained.

[Comparative Example 1]

M ₂ D _{24 .} 10 g of a side chain methylhydrogenpolysiloxane represented by ₆ D ^H ₂ and 58.9 g of a vinyl methylpolysiloxane having a terminal group represented by M ^Vi ₂ D ₁₅₀ (SiH group: 1 mol: 1.097 mol) , A platinum catalyst for feeding vinylmethylpolysiloxane was added in an amount of 2 ppm based on the total mass of the reaction system as platinum mass and the temperature was raised to gel at a temperature of about 60 캜. The residual SiH group amount was 0.005 mol / 100 g.

[Comparative Example 2]

M ₂ D _{24 . 6} D side chain type methyl hydrogen polysiloxane represented by 10g ^H ₂ and M ^Vi _2. 48 g (SiH group: vinyl group = 1 mole: 1.083 mole) of branched vinylmethylpolysiloxane represented by ₄ D _{147 .7} T _0.4 were mixed in 232 g of toluene (corresponding to 4 times the total mass of siloxane) A platinum catalyst for feeding methylpolysiloxane was added in an amount of 2 ppm based on the total weight of the reaction system as a platinum mass, and the temperature was elevated to gel at a temperature of about 70 캜. The residual SiH group amount was 0.007 mol / 100 g.

[Comparative Example 3]

M ₂ D _{24 . 6} D side chain type methyl hydrogen polysiloxane represented by 10g ^H ₂ and M ^Vi _2. 48 g (SiH group: vinyl group = 1 mole: 1.083 mole) of branched vinylmethylpolysiloxane represented by ₄ D _{147 .7} T _0.4 was added to 232 g of dimethylpolysiloxane represented by M ₂ D ₂₇ (side chain methylhydrogenpolysiloxane The platinum catalyst for the vinylmethylpolysiloxane was added in an amount of 2 ppm based on the total mass of the reaction system as platinum mass and the temperature was raised to about And gelled at a temperature of 70 ° C. The residual SiH group amount was 0.003 mol / 100 g.

Claims (13)

An organopolysiloxane having a structure represented by the following formula (1) and an organohydrogenpolysiloxane having a structure represented by the following formula (2) are mixed with the total of the polysiloxanes represented by the formulas (1) and (2) Average molecular weight of 5,000 to 300,000,000 obtained by a hydrosilylation reaction using a platinum group metal compound in a solvent of 8 times or more the mass of the organopolysiloxane crosslinking agent and containing 0.1 to 50 mol of a silane coupling agent per 1,000 mol of the siloxane unit Wherein the siloxane composition is dissolved in a solvent.
M _α M ^Vi _β D _γ D ^Vi _δ T _ε T ^Vi _ζ Q _η (1)
M _θ M ^H _ι D _κ D ^H _λ T _μ T ^H _ν (2)
(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is PSiO _3/2, M ^H is _{R 2 HSiO 1/2, D} H is RHSiO _2/2, T ^H is HSiO _3/2, Q is SiO _4/2, R is not having an aliphatic unsaturated bond, each independently An unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms, and P is an alkenyl group represented by - (CH ₂ ) _a -CH═CH ₂ (a is 0 or an integer of 1 to 6) δ, ζ, η, θ, ι, κ, λ, μ and ν are independently 0 or positive numbers and β, δ and ζ do not become 0 at the same time, β + δ + ζ≥2, and ι, λ and ν are not 0 at the same time, and ι + λ + ν≥2. The method according to claim 1,
Wherein 1?? +? +? +?? 1,000 in the formula (1) and 1?? +? +? 200 in the formula (2). 3. The method of claim 2,
1 in the formula (1) and 1? K? 200 in the formula (2). 4. The method according to any one of claims 1 to 3,
Characterized in that the solvent comprises an organic solvent selected from toluene, hexane, xylene and methyl ethyl ketone. 4. The method according to any one of claims 1 to 3,
Solvent octamethyl tetra siloxane, deca-methylpentanoyl siloxane, formula M ₂ D _n (M is R ₃ SiO _1/2 denotes a unit, D is R ₂ SiO _2/2 denotes a unit, R is an aliphatic, each independently An unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms having no unsaturated bond, and n is an integer of 0 to 200), and a linear siloxane represented by the formula M _{2 + m} D _n T _m is selected from the branched siloxane represented by (m, D, n are as described above, T represents an RSiO _3/2 unit, R is as defined above. m is an integer a. 1 to 10) ≪ / RTI > wherein the siloxane is an organosiloxane. The organopolysiloxane crosslinked product according to any one of claims 1 to 3,
M _{? '} M ^Vi _?' D _{? '} D ^Vi _?' T _{? '} T ^Vi _?' (3)
(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is ₃ PSiO _{/ 2} and, R are each independently an aliphatic unsaturated bond that the carbon atom number of 1 to 12 or an unsubstituted monovalent hydrocarbon group having no substitutions, and P is _{- (CH 2) a -CH =} CH 2 (a is 0 or an integer of 1 to 6), and each of α ', β', γ ', δ', ε 'and ζ' is independently 0 or a positive number, and α '+ β' +? '+?' +? '? 200), wherein the content of the organopolysiloxane is 0.1 to 40 times the mass of the crosslinked organopolysiloxane. 7. The method according to any one of claims 1 to 6,
The organopolysiloxane crosslinked with a kinematic viscosity 20mm ² / s (25 ℃) dimethyl siloxane polysiloxane composition, wherein a viscosity of 100~2,000,000mPa · s at 25 ℃ in the case where 30% by weight soluble in the hexanes. 8. The method according to any one of claims 1 to 7,
Wherein the viscosity at 25 DEG C of the organopolysiloxane crosslinked product in a toluene solution of 30 mass% is 50 to 1,000,000 mPa.s. 9. The method according to any one of claims 1 to 8,
The organosiloxane represented by the formula (1) has a weight average molecular weight of 260 to 74,874, and the organohydrogenpolysiloxane of the formula (2) has a weight average molecular weight of 208 to 15,414. . 10. The method according to any one of claims 1 to 9,
Wherein the residual SiH group content calculated from the amount of hydrogen gas generated by adding alkali is 0.001 mol / 100 g or less. An organopolysiloxane having a structure represented by the following formula (1) and an organohydrogenpolysiloxane having a structure represented by the following formula (2) are mixed with the total of the polysiloxanes represented by the formulas (1) and (2) An organopolysiloxane crosslinked product having a weight average molecular weight of 5,000 to 300,000,000 and containing 0.1 to 50 mol of a silane coupling agent per 1,000 mol of the siloxane unit by a hydrosilylation reaction using a platinum group metal compound in a solvent of 8 times or more the mass To obtain a siloxane composition.
M _α M ^Vi _β D _γ D ^Vi _δ T _ε T ^Vi _ζ Q _η (1)
M _θ M ^H _ι D _κ D ^H _λ T _μ T ^H _ν (2)
(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is PSiO _3/2, M ^H is _{R 2 HSiO 1/2, D} H is RHSiO _2/2, T ^H is HSiO _3/2, Q is SiO _4/2, R is not having an aliphatic unsaturated bond, each independently An unsubstituted or substituted monovalent hydrocarbon group of 1 to 12 carbon atoms, and P is an alkenyl group represented by - (CH ₂ ) _a -CH═CH ₂ (a is 0 or an integer of 1 to 6) δ, ζ, η, θ, ι, κ, λ, μ and ν are independently 0 or positive numbers and β, δ and ζ do not become 0 at the same time, β + δ + ζ≥2, and ι, λ and ν are not 0 at the same time, and ι + λ + ν≥2. 12. The method of claim 11,
An organopolysiloxane crosslinked product is obtained by using an organic solvent selected from toluene, hexane, xylene and methyl ethyl ketone as a solvent, an organopolysiloxane having a low viscosity is added as a solvent, and the organic solvent is distilled off under reduced pressure And removing by distillation by heating to obtain a composition containing no organic solvent. 13. The method of claim 12,
(3) < / RTI >< RTI ID = 0.0 >
M _{? '} M ^Vi _?' D _{? '} D ^Vi _?' T _{? '} T ^Vi _?' (3)
(Wherein, M is _{R 3 SiO 1/2, M} Vi is R ₂ PSiO _1/2, D is _{R 2 SiO 2/2, D} Vi is RPSiO _2/2, T has RSiO _3/2, T ^Vi is ₃ PSiO _{/ 2} and, R are each independently an aliphatic unsaturated bond that the carbon atom number of 1 to 12 or an unsubstituted monovalent hydrocarbon group having no substitutions, and P is _{- (CH 2) a -CH =} CH 2 (a is 0 or an integer of 1 to 6), and each of α ', β', γ ', δ', ε 'and ζ' is independently 0 or a positive number, and α '+ β' +? '+?' +? '+?'? 200), wherein the organopolysiloxane is an organopolysiloxane.